CN113964313B - Silicon-based negative electrode material and lithium ion battery - Google Patents
Silicon-based negative electrode material and lithium ion battery Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The application provides a silicon-based anode material and a lithium ion battery. The silicon-based anode material comprises: a silicon base material; an amorphous carbon coating layer; and a graphitized carbon coating layer, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon-based material. The method improves the circulation capacity of the silicon-based anode material, has simple preparation process and is suitable for large-scale industrial production.
Description
Related application
The application is a divisional application, the application number of the original application is 201980003461.5, the application date is 2019, 12 months and 30 days, and the invention is as follows: silicon-based negative electrode material and preparation method thereof, and lithium ion battery.
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-based negative electrode material and a lithium ion battery.
Background
In recent years, there has been a demand for higher energy density of lithium ion batteries, and thus higher capacity of negative electrode materials has been demanded. Currently, silicon oxide negative electrodes are beginning to be applied to power batteries and have a rapid growth trend.
Because of poor conductivity of silicon-oxygen materials, a layer of conductive material needs to be coated on the surface layer of the particles, and carbon coating is the most widely used at present. The carbon coating is not only beneficial to improving conductivity, but also has a certain constraint effect on the volume expansion of the silicon oxide particles after lithium intercalation.
At present, two methods are mainly used for carbon coating of silica particles: a liquid phase cladding method and a gas phase cladding method. Because silica particles are smaller and the polarity of surface valence bonds is large, the liquid phase coating method has larger problems in the aspects of particle dispersion and coating uniformity, and mass production scale is difficult to achieve. The Chemical Vapor Deposition (CVD) method can conveniently prepare composite particles with uniform coating and low particle adhesion, so that the current mainstream technology is CVD method preparation. The raw materials are placed in a rotary furnace, a rotary furnace and other equipment, 700-1050 ℃ is set, carbon-containing gas or steam is directly introduced, and a continuous carbon layer is formed on the surface layer of silicon oxide particles through pyrolysis, polycondensation and other reactions in the same reaction cavity.
Because of the disproportionation reaction of SiO at high temperature, the temperature of the conventional CVD coating method is generally lower than 1000 ℃, only a layer of amorphous carbon can be deposited on the surface of the particles, the carbon layer is loose, and the binding capacity of the coating layer on the particles is relatively small. When lithium is extracted from the silicon oxide particles, the volume change is huge, the coating layer is extremely easy to crack, a new SEI film is formed, and the SEI film gradually thickens along with the circulation, so that the results of serious gas production, poor circulation and the like of the lithium battery are caused. Due to the loose structure of the coating layer, the negative electrode active material is easy to deactivate after delithiation, i.e. the electrochemical activity is lost due to the fact that an effective conductive network cannot be formed due to poor electrical contact, so that the capacity of the lithium battery is attenuated too rapidly. While increasing the coating amount can alleviate cracking of the coating layer caused by volume change of the deintercalated lithium, too high a content of the coating layer will also result in lower capacity and first coulombic efficiency, further resulting in a decrease of energy density of the lithium ion battery prepared from the material.
Therefore, it is desirable to provide a new silicon-based negative electrode material and a method for manufacturing the same. .
Disclosure of Invention
The technical problem to be solved by the technical scheme is to provide a novel silicon-based negative electrode material and a manufacturing method thereof and provide a lithium ion battery comprising the silicon-based negative electrode material aiming at the defect that an amorphous carbon coating layer structure contained in the silicon-based negative electrode material in the prior art is easy to crack and influences battery performance.
One aspect of the present application provides a method for preparing a silicon-based anode material, including: in a non-oxidizing atmosphere, enabling a carbon source substance to pass through a pre-decomposition area to form decomposition products, wherein the carbon source substance comprises more than one of a gaseous carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; regulating and controlling the flow speed V of the decomposition products entering the reaction cavity of the deposition coating area G And the molar flow rate of the decomposition product and the mass ratio Mc/M of the silicon base material, so that the silicon base material and the decomposition product are subjected to deposition coating reaction in a deposition coating zone, an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon base material, and the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon base material, wherein V is more than or equal to 0.01 G ≤100，0.001≤Mc/M≤1，V G The unit is M/min, M C The unit is mol/min, M is the mass of the silicon-based substrate material in terms of carbon atoms, and the unit is kg.
In some embodiments of the present application, in a first condition: v is more than or equal to 10 G Forming a graphitized carbon coating layer on the surface of the silicon-based substrate material when Mc/M is more than or equal to 100,0.001 and less than 0.1; in a second condition: v is more than or equal to 0.01 G When Mc/M is more than or equal to 5,0.2 and less than or equal to 1, an amorphous carbon coating layer is formed on the surface of the silicon substrate material.
In some embodiments of the present application, the V is adjusted G And alternating the value of Mc/M between a first condition and a second condition, and forming an amorphous carbon coating layer and a graphitized carbon coating layer which are alternately coated on the surface of the silicon-based material.
In some embodiments of the present application, the gaseous carbon source comprises methane, ethane, ethylene, acetylene, propane, propylene, the vaporized carbon source comprises n-hexane, ethanol, benzene, and the atomized carbon source comprises polyethylene, polypropylene.
In some embodiments of the present application, during the deposition coating reaction, an N-containing species may also be introduced, including NH 3 One or more of acetonitrile, aniline, or butylamine.
In some embodiments of the present application, the non-oxidizing atmosphere refers to a reaction environment comprising any one or more of hydrogen, nitrogen, or an inert gas.
In some embodiments of the present application, the temperature of the pre-decomposed carbon source material ranges from 500 ℃ to 1500 ℃.
In some embodiments of the present application, the deposition coating reaction occurs at a temperature of 500 ℃ to 1100 ℃.
In some embodiments of the present application, the temperature of the pre-decomposed carbon source material ranges from 700 ℃ to 1300 ℃, and the temperature at which the deposition coating reaction occurs ranges from 650 ℃ to 1000 ℃.
In some embodiments of the present application, the silicon-based material comprises metallurgical silicon, silicon oxide SiOx, 0.ltoreq.x.ltoreq.1.5, and one or more mixtures of porous silicon, and the median particle size of the silicon-based material ranges from 1 μm to 20 μm.
In some embodiments of the present application, the silicon-based material further comprises a compound having the formula MSiOy, wherein 0.85< y.ltoreq.3.5; m is any one or more of Li, na, mg, al, fe, ca.
The application also provides a silicon-based anode material, comprising: a silicon base material; an amorphous carbon coating layer; and a graphitized carbon coating layer, wherein the amorphous carbon coating layer or graphitized carbon coating layer is directly coated on the surface of the silicon-based substrate material.
In some embodiments of the present application, the amorphous carbon coating has a raman spectrum Id/Ig >0.7 and the graphitized carbon coating has a raman spectrum Id/Ig < 0.5.
In some embodiments of the present application, the amorphous carbon coating layer is heated under an air atmosphere at an oxidation onset temperature of 400 ℃ or less and the graphitized carbon coating layer has an onset oxidation temperature of 450 ℃ or more.
In some embodiments of the present application, the amorphous carbon coating layer is doped with nitrogen atoms, and the graphitized carbon coating layer is doped with nitrogen atoms.
In some embodiments of the present application, the surface of the silicon-based material includes two or more amorphous carbon coating layers and two or more graphitized carbon coating layers, and the two or more amorphous carbon coating layers and the two or more graphitized carbon coating layers are alternately arranged.
In some embodiments of the present application, the amorphous carbon coating layers each have a thickness ranging from 1nm to 20nm, and the graphitized carbon coating layers each have a thickness ranging from 1nm to 20nm.
In some embodiments of the present application, the sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon-based substrate material is 1nm to 1000nm.
In some embodiments of the present application, the amorphous carbon coating layer is 1-10% by mass of the silicon-based anode material, and the graphitized carbon coating layer is 1-10% by mass of the silicon-based anode material.
In some embodiments of the present application, the silicon-based material comprises metallurgical silicon, silicon oxide SiOx (0.ltoreq.x.ltoreq.1.5), one or more mixtures of porous silicon, and the median particle size of the silicon-based material ranges from 1 μm to 20 μm.
In some embodiments of the present application, the silicon-based material further comprises a compound having the formula MSiOy, wherein 0.85< y.ltoreq.3.5; m is any one or more of Li, na, mg, al, fe, ca.
The application also provides a lithium ion battery, and the negative electrode of the lithium ion battery comprises the silicon-based negative electrode material.
According to the silicon-based anode material, the amorphous carbon coating layer and the graphitized carbon coating layer are formed on the surface of the silicon-based substrate material, the amorphous carbon coating layer is of a loose amorphous carbon structure, a buffering effect is achieved in lithium intercalation expansion of the silicon-based substrate material, the graphitized carbon coating layer plays a certain binding effect on lithium intercalation expansion of the silicon-based substrate material, cracking of the coating layer and inactivation of active substances in a lithium deintercalation process of the silicon-based substrate material are prevented, the charge-discharge circulation capacity of the silicon-based anode material is improved, and the service life of a secondary battery is further prolonged.
In addition, the embodiment of the application also provides a manufacturing method of the silicon-based anode material, and the whole preparation process of the method is simple to operate and is very suitable for industrial production.
Additional features of the application will be set forth in part in the description which follows. The following drawings and examples will be described in such detail as will become apparent to those of ordinary skill in the art from this disclosure. The inventive aspects of the present application may be best explained by practicing or using the methods, instrumentalities and combinations thereof set forth in the detailed examples discussed below.
Drawings
The following figures describe in detail exemplary embodiments disclosed in the present application. Wherein like reference numerals refer to like structure throughout the several views of the drawings. Those of ordinary skill in the art will understand that these embodiments are non-limiting, exemplary embodiments, and that the drawings are for illustration and description purposes only and are not intended to limit the scope of the present disclosure, as other embodiments may equally accomplish the inventive intent in this application. It should be understood that the drawings are not to scale. Wherein:
fig. 1 is an SEM image of a silicon-based anode material provided in an embodiment of the present application;
fig. 2 is a raman spectrum diagram of an amorphous carbon coating layer and a graphitized carbon coating layer in a silicon-based anode material provided in an embodiment of the present application.
Detailed Description
The following description provides specific applications and requirements to enable any person skilled in the art to make and use the teachings of the present application. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, the present disclosure is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
The technical scheme of the invention is described in detail below with reference to the examples and the accompanying drawings.
In one aspect, the present application provides a silicon-based negative electrode material, which is used for lithium ion batteries. The silicon-based anode material comprises: a silicon base material; an amorphous carbon coating layer; and a graphitized carbon coating layer, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon-based material.
That is, an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon base material. In some embodiments of the present application, the amorphous carbon coating layer is directly coated on the surface of the silicon substrate material, and the graphitized carbon coating layer is coated on the surface of the amorphous carbon coating layer. In other embodiments of the present application, the graphitized carbon coating layer is directly coated on the surface of the silicon-based substrate material, and the amorphous carbon coating layer is coated on the surface of the graphitized carbon coating layer. The "coating" in the embodiments of the present application may be a partial coating or a complete coating, and the degree of coating of the "coating" may be different according to the manufacturing process of the silicon-based anode material.
For example, the total coating thickness of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 500nm, wherein the amorphous carbon coating layer with the total thickness of 400nm is coated on the surface of the silicon substrate material (the amorphous carbon coating layer with the total thickness of 400nm can comprise a plurality of single amorphous carbon coating layers with the single layer thickness of 1nm to 20 nm), the graphitized carbon coating layer with the total thickness of 100nm is coated on the surface of the amorphous carbon coating layer (the graphitized carbon coating layer with the total thickness of 100nm can comprise a plurality of single graphitized carbon coating layers with the single layer thickness of 1nm to 20 nm), and the coating degree of the amorphous carbon coating layer or the graphitized carbon coating layer is relatively high and is close to full coating. In the examples of the present application, the amorphous carbon coating layer or the graphitized carbon coating layer is considered to form a fully coated structure when the thickness thereof reaches about 5 nm.
For another example, the total coating thickness of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 30nm, wherein the surface of the silicon substrate material is coated with 5nm of graphitized carbon coating layer, 3nm of amorphous carbon coating layer, 4nm of graphitized carbon coating layer, 2nm of amorphous carbon coating layer, 10nm of graphitized carbon coating layer and 6nm of amorphous carbon coating layer in sequence.
In the above embodiment, the surface of the silicon base material includes two or more amorphous carbon coating layers and two or more graphitized carbon coating layers, and the two or more amorphous carbon coating layers and the two or more graphitized carbon coating layers are alternately arranged. In the structure in which the amorphous carbon coating layer and the graphitized carbon coating layer are alternately arranged, the amorphous carbon coating layer or the graphitized carbon coating layer can be directly coated on the surface of the silicon substrate material.
Because the amorphous carbon coating layer is of a loose amorphous carbon structure, the amorphous carbon coating layer plays a role in buffering in lithium intercalation expansion of a silicon-based substrate material, and the graphitized carbon coating layer is of a crystal-form carbon structure with high graphitization degree, plays a certain role in binding the lithium intercalation expansion of the silicon-based substrate material, and prevents cracking of the coating layer and inactivation of active substances in the lithium intercalation process of the silicon-based substrate material, so that the alternately arranged amorphous carbon structure and graphitized carbon coating structure can better adjust the charge and discharge performance of the silicon-based anode material, and the cycle life of a battery is prolonged.
In some embodiments of the present application, the thickness of each amorphous carbon coating layer ranges from 1nm to 20nm, and the thickness of each graphitized carbon coating layer ranges from 1nm to 20nm. The sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon-based substrate material is 2 nm-1000 nm. For example, if the sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon base material is 300nm, the surface of the silicon base material includes amorphous carbon coating layers having a thickness of 10nm and graphitized carbon coating layers having a thickness of 10nm alternately arranged 15 times.
In some embodiments of the present application, the amorphous carbon coating layer is 1-10% by mass of the silicon-based anode material, and the graphitized carbon coating layer is 1-10% by mass of the silicon-based anode material. The amorphous carbon coating layer and the graphitized carbon coating layer account for 2-20% of the total mass percent of the silicon-based anode material. When the outermost layer of the silicon-based anode material is an amorphous carbon coating layer, the specific surface area of the silicon-based anode material is generally high (1-20 m 2 And/g), the specific surface area of the silicon-based anode material is generally low (0.1-15 m) when the graphitized carbon coating layer is at the outermost layer of the silicon-based anode material 2 /g)。
In some embodiments of the present application, the amorphous carbon coating layer may be 5%,3%,8% by mass in the silicon-based anode material, and the graphitized carbon coating layer may be 4%,6%,9%, or 5%,3%,8% by mass in the silicon-based anode material. That is, the amorphous carbon coating layer and the graphitized carbon coating layer may be the same or different in mass percentage content in the silicon-based anode material.
In an embodiment of the present application, the amorphous carbon coating layer has a raman spectrum Id/Ig >0.7 and the graphitized carbon coating layer has a raman spectrum Id/Ig <0.5 as determined by raman spectroscopy. In the heating test under the air atmosphere, the oxidation initial temperature of the amorphous carbon coating layer is less than or equal to 400 ℃, and the initial oxidation temperature of the graphitized carbon coating layer is more than or equal to 450 ℃. Since the structure of the silicon-based anode material plays a decisive role in the oxidation initiation temperature, the oxidation initiation temperature of the amorphous carbon coating layer and the graphitized carbon coating layer represents the coating layer property of the silicon-based anode material.
The intensity of the D peak represents the disorder degree of the carbon layer in the Raman spectrum, the intensity of the G peak represents the ordering degree of the material, namely Id/Ig can effectively represent the graphitization degree of the carbon layer, and a great relationship exists between the graphitization degree of the graphitized carbon coating layer and the performance of the silicon-based anode material. The smaller the raman spectrum value of the graphitized carbon coating layer is, the higher the graphitization degree of the graphitized carbon coating layer is, namely, the graphitized carbon coating layer has a more complete graphite lamellar structure, so that the better the graphitized carbon coating layer has a constraint effect on lithium intercalation expansion of a silicon-based substrate material, and is beneficial to forming a stable SEI film on the surface of a silicon-based negative electrode material when the graphitized carbon coating layer is applied to a lithium ion battery, thereby reducing consumption of active lithium in a circulation process and improving the circulation performance of the lithium ion battery. In an oxidizing atmosphere, the amorphous carbon has a lower oxidation initiation temperature point and the graphitized carbon has a higher oxidation initiation temperature point.
In some embodiments of the present application, the amorphous carbon coating layer may be further doped with nitrogen atoms. The graphitized carbon coating layer may be doped with nitrogen atoms. The nitrogen atom may be derived from N-containing species such as NH 3 One or more of acetonitrile, aniline, or butylamine. The nitrogen atoms are added into the amorphous carbon coating layer and the graphitized carbon coating layer, so that the charging and discharging capacity of the silicon-based anode material can be further improved, and the conductivity of the material can be further improved after nitrogen doping, so that the internal resistance of the battery is reduced, and the high-current charging and discharging capacity of the battery is further ensured.
In some embodiments of the present application, the silicon-based material comprises metallurgical silicon, silicon oxide SiOx (0.ltoreq.x.ltoreq.1.5), one or more mixtures of porous silicon, and the median particle size of the silicon-based material ranges from 1 μm to 20 μm. In some embodiments of the present application, the silicon-based material further comprises a compound having the formula MSiOy, wherein 0.85< y.ltoreq.3.5; m is any one or more of Li, na, mg, al, fe, ca.
According to the silicon-based anode material, the amorphous carbon coating layer and the graphitized carbon coating layer are formed on the surface of the silicon-based substrate material, so that the charge-discharge circulation capacity of the silicon-based anode material is improved, and the service life of the secondary battery is further prolonged.
In addition, the embodiment of the application also provides a manufacturing method of the silicon-based anode material, and the whole preparation process of the method is simple to operate and is very suitable for industrial production.
The embodiment of the application provides a preparation method of a silicon-based anode material, which comprises the following steps: in a non-oxidizing atmosphere, enabling a carbon source substance to pass through a pre-decomposition area to form decomposition products, wherein the carbon source substance comprises more than one of a gaseous carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; regulating and controlling the flow velocity V of the decomposition products entering the reaction cavity of the deposition coating area G And the molar flow rate of the decomposition product and the mass ratio Mc/M of the substrate material, so that the silicon substrate material and the decomposition product are subjected to deposition coating reaction in a deposition coating region, an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon substrate material, and the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material, wherein V is more than or equal to 0.01 G ≤100，0.001≤Mc/M≤1，V G The unit is M/min, M C The unit is mol/min, M is the mass of the silicon-based substrate material in terms of carbon atoms, and the unit is kg.
The preparation of the silicon-based anode material can use coating equipment such as a rotary furnace, a rotary furnace and the like to achieve the purpose of uniform coating. The coating apparatus may be configured to include a pre-decomposition zone and a deposition coating zone, both of which include a reaction chamber. Wherein the pre-decomposition area is used for pre-decomposing carbon source substances. For example, the carbon source material is introduced into a pre-decomposition area of the coating device, and in a non-oxidizing atmosphere, the carbon source material is subjected to pyrolysis, cracking, polycondensation and other reactions to become a gaseous material. Wherein, low molecular weight substances in the carbon source substances are medium and large molecular weight substances through pyrolysis, polycondensation, addition and other reactions; the cleavage of high molecular weight materials into small and medium molecular weight materials is also accompanied by reactions such as pyrolysis, polycondensation, addition, etc.
The gas providing the non-oxidizing atmosphere includes, for example, any one or more of hydrogen, nitrogen, or inert gas for use as a shielding gas, carrier gas, and dilution gas for the pre-decomposition zone reaction.
The gaseous carbon source substance comprises hydrocarbon which is gaseous at room temperature and aldehyde which is gaseous at room temperature, the gaseous carbon source substance comprises methane, ethane, ethylene, acetylene, propane and propylene,
the vaporized carbon source material is a carbon-containing material which is liquid at room temperature and is gaseous at room temperature or above but below the temperature of the pre-decomposition zone, and comprises n-hexane, ethanol and benzene.
The atomized carbon source material is a material which is difficult to evaporate by heating, and can be made into small droplets by an atomizing device, for example, a material which is liquid at a temperature lower than that in the pre-decomposition region. The atomized carbon source substance comprises polyethylene and polypropylene.
In some embodiments of the present application, the flow velocity V of the decomposition products into the reaction chamber of the deposition coating zone is controlled G And the molar flow rate of the decomposition product and the mass ratio Mc/M of the base material are used for carrying out deposition coating reaction on the silicon base material and the decomposition product in a deposition coating zone, so that an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon base material. Wherein V is 0.01-V G ≤100，0.001≤Mc/M≤1，V G The unit is M/min, M C The unit is mol/min, M is the mass of the silicon-based substrate material in terms of carbon atoms, and the unit is kg.
In a first condition: v is more than or equal to 10 G Forming a graphitized carbon coating layer on the surface of the silicon-based substrate material when Mc/M is more than or equal to 100,0.001 and less than 0.1; in a second condition: v is more than or equal to 0.01 G When Mc/M is more than or equal to 5,0.2 and less than or equal to 1, an amorphous carbon coating layer is formed on the surface of the silicon substrate material. That is, the manufacturing process of the silicon-based anode material in the embodiment of the application can adjust the thickness and the alternate coating condition of the formed amorphous carbon coating layer and graphitized carbon coating layer only by adjusting the flow rate and the mass of the reactant and the reaction time. After the thickness of the coating layer reaches a set value, the flow and the mass of the reactant are quickly adjusted, and the coating layer can be switched to another coating layer. Of course, in a practical process, the flow rate and mass adjustment speed of the reactants are set to be slow, and there may be a composite coating layer including both amorphous carbon coating layer and graphitized carbon coating layer.
That is, by controllingV G (m/min)、Mc/M(M C In mol/min, M is the mass of the silicon-based substrate material in terms of carbon atoms, and kg), the crystal structure of the coating layer can be controlled, thereby obtaining an amorphous carbon coating layer and a graphitized carbon coating layer. Meanwhile, the mass percentage content of the carbon coating layer is adjusted by combining the reaction time.
The running speed of the silicon substrate material and the flowing speed of the decomposition products entering the reaction cavity are adjusted to ensure that a uniform and continuous amorphous carbon coating layer and graphitized carbon coating layer are obtained in the reaction process, and meanwhile, the loss of materials is reduced as much as possible.
In some embodiments of the present application, the V is adjusted G And alternating the Mc/M value between the first condition and the second condition, and forming an amorphous carbon coating layer and a graphitized carbon coating layer which are alternately coated on the surface of the silicon-based substrate material. Because the amorphous carbon coating layer is of a loose amorphous carbon structure, the amorphous carbon coating layer plays a role in buffering in lithium intercalation expansion of a silicon-based substrate material, and the graphitized carbon coating layer is of a crystal-form carbon structure with high graphitization degree, plays a certain role in binding the lithium intercalation expansion of the silicon-based substrate material, and prevents cracking of the coating layer and inactivation of active substances in the lithium intercalation process of the silicon-based substrate material, so that the alternately arranged amorphous carbon structure and graphitized carbon coating structure can better adjust the charge and discharge performance of the silicon-based anode material, and the cycle life of a battery is prolonged.
In some embodiments of the present application, the atomized carbon source is thermally decomposed in the pre-decomposition zone and the pyrolysis product molar flow rate M is calculated C CO can be measured after oxidation combustion 2 The content is determined by the method. And gaseous and steam carbon source, the molar flow rate M of pyrolysis products is directly determined according to the molecular structure of the inlet gas C 。
In some embodiments of the present application, during the deposition coating reaction, an N-containing species may also be introduced, including NH 3 One or more of acetonitrile, aniline, or butylamine.
In the embodiment of the application, the temperature range of the pre-decomposed carbon source substance is set to 500-1500 ℃, preferably 700-1300 ℃, so that the carbon source substance can be changed into a gas state in the pre-decomposition area, and pyrolysis or polycondensation reaction can be rapidly performed to form a pre-decomposition area product capable of rapidly performing subsequent coating reaction. In the pre-decomposition zone, the desired temperature can be reached using conventional heating means or using microwaves or radio frequencies, etc. However, the C-containing substance can be ionized by adopting a microwave heating mode, so that the pre-decomposition temperature can be obviously reduced and the pre-decomposition efficiency can be improved compared with other heating modes.
In some embodiments of the present application, after the gaseous carbon source material passes through the pre-decomposition area, dehydrogenation, free radical addition, etc. reactions take place, and become linear or aromatic compounds with larger relative molecular mass and lower gibbs free energy, after the vaporized carbon source material passes through the pre-decomposition area, dehydrogenation (cracking), free radical addition, etc. reactions take place, and become linear or aromatic compounds, and after the atomized carbon source material passes through the pre-decomposition area, cracking, free radical addition, etc. reactions take place, and become linear or aromatic compounds.
In the embodiment of the application, after the pre-decomposition reaction, the mixed gas passing through the pre-decomposition area is a decomposition product, and the decomposition product comprises non-oxidizing gas introduced into the reaction atmosphere and carbon source substances after the pre-decomposition. In some embodiments of the present application, the carbon source material (gaseous state) after the pre-decomposition accounts for 1-70% of the volume of the decomposition product, and the pre-decomposition reaction step can make the reaction temperature control more flexible in the manufacturing method of the silicon-based anode material, which is favorable for controlling the reaction progress of decomposition, addition, etc. of the carbon source material, and has small temperature interference to the cladding region.
And then, introducing the decomposition products into a deposition coating region of the coating equipment, so that a silicon substrate material and the pre-decomposed carbon source substance are subjected to deposition coating reaction, and an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon substrate material, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material.
In some embodiments of the present application, the temperature at which the deposition coating reaction occurs is 500 ℃ to 1100 ℃, preferably, the temperature at which the deposition coating reaction occurs is 650 ℃ to 1000 ℃. In the process of the deposition coating reaction, if the temperature is too low, the ratio of C/H of the surface coating layer of the anode material is too high, so that the conductivity is poor, and the performance is affected. If the temperature is too high, the silicon oxide in the silicon base material is easily disproportionated excessively, and the capacity and cycle performance of the silicon-based anode material are affected.
The silicon base material comprises metallurgical silicon and silicon oxide SiOx (x is more than or equal to 0 and less than or equal to 1.5), one or a mixture of more of porous silicon, and the median particle size of the silicon base material ranges from 1 mu m to 20 mu m. In some embodiments of the present application, the silicon-based material further comprises a compound of the formula MSiOy, wherein (0.85 < y.ltoreq.3.5; M is any one or more of Li, na, mg, al, fe, ca).
During the deposition coating reaction, N-containing substances including NH can be introduced 3 One or more of acetonitrile, aniline, or butylamine. The N-containing material is introduced to obtain an amorphous carbon coating layer and a graphitized carbon coating layer doped with N atoms. The amorphous carbon coating layer and the graphitized carbon coating layer doped with N atoms can further improve the charge-discharge capacity of the silicon-based anode material, because the amorphous carbon coating layer and the graphitized carbon coating layer can further improve the conductivity of the material after nitrogen doping, thereby reducing the internal resistance of the battery and further ensuring the high-current charge-discharge capacity of the battery.
In some embodiments of the present application, the mass percentage of the amorphous carbon coating layer and the graphitized carbon coating layer in the silicon-based anode material is, for example, 0.01-99:1, preferably, the amorphous carbon coating layer accounts for 10-90%, for example, 20%,30%,40%,50%,60%,70%,80%, etc.
In some embodiments of the present application, the silicon-based negative electrode material has more than one amorphous carbon coating layer and/or more than one graphitized carbon coating layer on the surface of the silicon-based substrate material, and further, the more than one amorphous carbon coating layer and the more than one graphitized carbon coating layer are alternately arranged.
For example, methane with the flow rate of 10m/min is firstly introduced into the pre-decomposition area, nitrogen is used as protective gas, the reaction temperature is 1000 ℃, the reaction is stopped after 180 minutes of introduction, n-hexane with the flow rate of 1m/min is continuously introduced into the pre-decomposition area, nitrogen is continuously used as protective gas, and the reaction is stopped after 120 minutes of introduction. The process of introducing methane and n-hexane can be alternately performed.
In another embodiment, propylene with the flow rate of 5m/min is firstly introduced into the pre-decomposition area, ar is used as a protective gas, the reaction is stopped after 300 minutes of introduction at the reaction temperature of 1000 ℃, the polypropylene melt with the flow rate of 0.1m/min is continuously introduced into the pre-decomposition area, ar is used as the protective gas, and the reaction is stopped after 240 minutes of introduction. The propylene and polypropylene passing processes may be alternated.
In a further embodiment of the present application, hydrogen is used as a shielding gas, and a mixed gas of ethane and ethanol is introduced into the pre-decomposition area, wherein the flow rate of ethane and ethanol is 50m/min, the reaction temperature is 1200 ℃, and the reaction is stopped after 100 minutes.
Example 1
1kg of silicon oxide SiOx (x=0.9) with a median particle size of 5 μm is selected as a silicon substrate material by using a rotary furnace comprising a pre-decomposition zone and a deposition coating zone, and a flow rate V is introduced into the pre-decomposition zone with nitrogen as a shielding gas G A mixture of ethane gas and ethanol vapor with a molar ratio of ethane to ethanol of 1:1 and a reaction temperature of 900 ℃ and M is adjusted c And (3) introducing M=0.25 mol/min into a deposition coating area of the rotary furnace, wherein the temperature of the deposition coating area is 900 ℃, and the total reaction time is 20min, so as to form the silicon-based anode material S1-1.
Continuously reacting the S1-1 material at the same temperature, and introducing V G Methane and ethylene mixed gas with 10M/min, wherein the volume ratio of methane to ethylene is 3:1, M is controlled c and/M=0.05, wherein the reaction time is 120min, and the silicon-based anode material S1-2 is formed.
Continuously reacting the S1-2 material at the same temperature, and introducing V G ＝5And (3) benzene vapor in M/min, wherein Mc/M=0.5 is controlled, and the reaction time is 10min, so that the silicon-based anode material S1-3 is formed.
Continuously reacting the S1-3 material at the same temperature, and introducing V G The silicon-based anode material S1-4 was formed by controlling Mc/m=0.25 and the reaction time to be 10min, which is a mixture of ethane gas and ethanol vapor with a molar ratio of ethane to ethanol of 1:1.
Example 2
1kg of silicon oxide SiOx (X=0.9) having a median particle size of 8 μm was selected as a silicon base material by using the same equipment as in example 1, and a flow rate V was introduced into a pre-decomposition zone with nitrogen as a shielding gas G And (2) introducing mixed gas of methane and ethylene with the volume ratio of methane to ethylene of 10M/min to 1, the reaction temperature of 900 ℃, mc/M=0.05 mol/min, and the total reaction time of 120min at the temperature of 900 ℃ into a deposition coating area of the rotary furnace to form the silicon-based anode material S2-1.
Continuously reacting the S2-1 material at the same temperature, and introducing V G Ethane gas and ethanol vapor mixture of 1M/min, wherein the molar ratio of ethane to ethanol is 1:1, M is controlled c and/M=0.25, wherein the reaction time is 10min, and the silicon-based anode material S2-2 is formed.
Continuously reacting the S2-2 material at the same temperature, and introducing V G Methane and ethylene mixed gas with 10M/min, wherein the volume ratio of methane to ethylene is 3:1, M is controlled c and/M=0.05, wherein the reaction time is 120min, and the silicon-based anode material S2-3 is formed.
Continuously reacting the S2-3 material at the same temperature, and introducing V G Benzene vapor of 5M/min, control M c and/M=0.5, wherein the reaction time is 10min, and the silicon-based anode material S2-4 is formed.
Specific process conditions for examples 3 to 6 are referred to in table 1.
Comparative example 1
1kg of silicon oxide SiOx (x=0.9) with a median particle size of 5 μm is selected as a silicon base material, nitrogen is used as a protective gas, the reaction temperature is set to 900 ℃, and the reaction temperature is controlledM preparation c And/m=0.5, and the reaction time is 30min, so as to form the silicon-based anode material D1.
Comparative example 2
1kg of silicon oxide SiOx (x=0.9) with a median particle size of 5 μm was selected as a silicon base material, nitrogen was used as a shielding gas, the reaction temperature was set at 1000℃and M was controlled c And/m=0.05, and the reaction time is 300min, so as to form the silicon-based anode material D2.
Other process conditions for comparative examples and comparative example 2 are also referred to table 1.
Table 1 is the process conditions of the respective steps of the preparation methods of silicon-based anode materials of examples 1 to 6 and comparative examples 1 and 2, and specific process descriptions refer to the text portions of examples 1 and 2 and comparative examples 1 and 2.
Table 2 shows the thicknesses of the amorphous carbon coating layer (AC) and graphitized carbon coating layer (GC) of the silicon-based anode materials formed by the preparation methods of the silicon-based anode materials of examples 1 to 6 and comparative examples 1 and 2, the mass percentage content of carbon element, and raman spectrum detection data. The silicon-based anode material is used as the anode material of the lithium battery, the electrochemical performance of the anode material is detected according to the data in the table, as shown in fig. 2 (capacity mAh/g, efficiency% and 30-week cycle capacity retention), wherein the efficiency% refers to the first coulombic efficiency%), when the silicon-based anode material formed by the preparation method of the silicon-based anode material is used as the anode material of the lithium battery, the capacity mAh/g under unit mass, the first coulombic efficiency and the 30-week cycle capacity retention are far higher than those of the silicon-based anode material in a comparison test.
Fig. 1 and fig. 2 of the present application also provide SEM images of the silicon-based anode material described in the embodiments of the present application, and raman spectra of the amorphous carbon coating layer and the graphitized carbon coating layer in the silicon-based anode material provided in the embodiments of the present application. As can be seen from fig. 1, the silicon-based anode material particles having the amorphous carbon coating layer and the graphitized carbon coating layer on the surface thereof according to the embodiment of the present application are uniformly dispersed. As can be seen from fig. 2, in the silicon-based anode material, the amorphous carbon coating layer and the graphitized carbon coating layer each have a G peak and a D peak, and the peak intensities corresponding to the amorphous carbon coating layer and the graphitized carbon coating layer are different. Wherein line 1 is a graphitized carbon coating and line 2 is an amorphous carbon coating. The Raman spectrum Id/Ig of the amorphous carbon coating layer is 0.92, and the Raman spectrum Id/Ig of the graphitized carbon coating layer is 0.43.
In view of the foregoing, it will be evident to a person skilled in the art that the foregoing detailed disclosure may be presented by way of example only and may not be limiting. Although not explicitly described herein, those skilled in the art will appreciate that the present application is intended to embrace a variety of reasonable alterations, improvements and modifications to the embodiments. Such alterations, improvements, and modifications are intended to be proposed by this disclosure, and are intended to be within the spirit and scope of the exemplary embodiments of this disclosure.
It should be understood that the term "and/or" as used in this embodiment includes any or all combinations of one or more of the associated listed items.
It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used herein, specify the presence of stated features, integers, steps, operations, materials, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, materials, components, and/or groups thereof.
Furthermore, the exemplary embodiments are described by reference to cross-sectional illustrations and/or plan illustrations that are idealized exemplary illustrations.
Claims (11)
1. A silicon-based anode material comprising:
a silicon base material;
an amorphous carbon coating layer; and
a graphitized carbon coating layer having a raman spectrum Id/Ig <0.5;
the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon-based substrate material, and when the thickness of the amorphous carbon coating layer or the graphitized carbon coating layer reaches 5nm, the coating is of a full coating structure.
2. The silicon-based anode material of claim 1, wherein the raman spectrum Id/Ig of the amorphous carbon coating layer is >0.7.
3. The silicon-based anode material according to claim 1, wherein the amorphous carbon coating layer has an oxidation initiation temperature of 400 ℃ or less and the graphitized carbon coating layer has an initiation oxidation temperature of 450 ℃ or more when heated under an air atmosphere.
4. The silicon-based anode material according to claim 1, wherein the amorphous carbon coating layer is doped with nitrogen atoms, and the graphitized carbon coating layer is doped with nitrogen atoms.
5. The silicon-based anode material according to claim 1, wherein the surface of the silicon-based material comprises two or more layers of the amorphous carbon coating layer and two or more layers of the graphitized carbon coating layer, and the two or more layers of the amorphous carbon coating layer and the two or more layers of the graphitized carbon coating layer are alternately arranged.
6. The silicon-based anode material according to claim 1 or 5, wherein the thickness of each of the amorphous carbon coating layers ranges from 1nm to 20nm, and the thickness of each of the graphitized carbon coating layers ranges from 1nm to 20nm.
7. The silicon-based anode material according to claim 1, wherein the sum of thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon-based substrate material is 1nm to 1000nm.
8. The silicon-based anode material according to claim 1, wherein the amorphous carbon coating layer is 1-10% by mass of the silicon-based anode material, and the graphitized carbon coating layer is 1-10% by mass of the silicon-based anode material.
9. The silicon-based negative electrode material according to claim 1, wherein the silicon-based substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx,0< x.ltoreq.1.5, porous silicon, and the median particle size of the silicon-based substrate material is in the range of 1 μm to 20 μm.
10. The silicon-based anode material of claim 2, wherein the silicon-based substrate material further comprises a compound of the general formula MSiOy, wherein 0.85< y +.3.5; m is any one or more of Li, na, mg, al, fe, ca.
11. A lithium ion battery, characterized in that the negative electrode of the lithium ion battery comprises the silicon-based negative electrode material according to any one of claims 1 to 10.
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